EP0114982B1 - Äussere Anstrichmittel für optische Fasern mit einer Pufferschicht - Google Patents

Äussere Anstrichmittel für optische Fasern mit einer Pufferschicht Download PDF

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Publication number
EP0114982B1
EP0114982B1 EP83112164A EP83112164A EP0114982B1 EP 0114982 B1 EP0114982 B1 EP 0114982B1 EP 83112164 A EP83112164 A EP 83112164A EP 83112164 A EP83112164 A EP 83112164A EP 0114982 B1 EP0114982 B1 EP 0114982B1
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EP
European Patent Office
Prior art keywords
coating composition
recited
coating
acrylate
molecular weight
Prior art date
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Expired
Application number
EP83112164A
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English (en)
French (fr)
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EP0114982A2 (de
EP0114982A3 (en
Inventor
Timothy E. Bishop
George Pasternack
Orvid R. Cutler, Jr.
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Koninklijke DSM NV
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DeSoto Inc
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Publication of EP0114982A3 publication Critical patent/EP0114982A3/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
    • C08F299/065—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes from polyurethanes with side or terminal unsaturations
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/026—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from the reaction products of polyepoxides and unsaturated monocarboxylic acids, their anhydrides, halogenides or esters with low molecular weight
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S525/92—Polyurethane having terminal ethylenic unsaturation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S525/922—Polyepoxide polymer having been reacted to yield terminal ethylenic unsaturation

Definitions

  • This invention relates to the coating of optical fibers using radiation-curable coating compositions, and more particularly to the provision of ultraviolet curable topcoating compositions which are used to protect the primary of buffer coating which is applied to protect the glass surface of the optical fibers.
  • the primary coating is also referred to as a buffer coating because it intervenes between the glass fiber and the topcoating. Since the buffer coating is also referred to as a primary coating, the topcoating may also be termed a secondary coating.
  • Optical glass fibers are acquiring increasing importance for communication purposes, but in order to use the glass fibers it is necessary to protect the glass surface from moisture and from abrasion. This is done by coating the glass fiber immediately following its formation. Solvent solution coatings and extrusions have been applied, but these present problems which have been solved to a considerable extent by the employment of ultraviolet light-curable coating compositions.
  • a radiation-curable coating composition adapted to be applied to buffer-coated optical fibers to apply an adherent topcoat having greater toughness and greater hardness than said buffer coating
  • which comprises (1) from 25 to 70% of the coating composition of diethylenic-terminated polyurethane which may include urea linkages, said polyurethane being based on a diisocyanate having an average molecular weight of from 400 to 5000, preferably from 800 to 2500; (2) from 5% to 40% of the coating composition of a diethylenically unsaturated ester of a diglycidylether of a bisphenol, said ether having a 1,2-epoxyequivatency of at least 1.4 and a molecular weight of up to 1000; said ether being preferably a diglycidyl ether of bisphenol A, and having an average molecular weight less than 400; and (3) from 5% to 30% of the coating composition of liquid radiation curable monoethylenically unsaturated monomer, the
  • This combination of radiation-curable components provides great physical toughness in combination with considerable hardness in an adherent coating, and the monoethylenically unsaturated monomer that provides a homopolymer having a high glass transition temperature (hereinafter called “high Tg monomer”) reduces the viscosity while increasing the speed of radiation cure.
  • high Tg monomer the monoethylenically unsaturated monomer that provides a homopolymer having a high glass transition temperature
  • the high Tg monomers used herein are illustrated by dimethyl acrylamide, N-vinyl pyrrolidone, isobornyl acrylate and dicylopentenyl acrylate.
  • N-vinyl pyrrolidone is especially preferred because it is far better at lowering viscosity while simultaneously increasing the speed of radiation cure.
  • N-vinyl pyrrolidone While it is known that N-vinyl pyrrolidone, and to a lesser extent the other monomers listed, are capable of reducing the viscosity and increasing the cure speed of radiation curable coatings, it was not known that relatively large amounts of high Tg monomers would increase the hardness of the compositions under consideration while retaining the generally tough, moderate modulus character of the cured compositions. Thus, N-vinyl pyrrolidone, and to a lesser extent the other listed high Tg monomers, accomplish several commercially important objectives at the same time.
  • diacrylate-terminated polyurethanes these are formed by providing acrylate-functional terminal groups on a diisocyanate-terminated product having a molecular weight in the range of 400 to 5000, preferably 800 to 2500. While several production procedures are available, the diisocyanate-terminated product can be described as the reaction product of an organic diisocyanate with an aliphatic molecule having two isocyanate-reactive hydrogen atoms, as may be provided by OH, SH, or NH 3 groups. These diisocyanate-terminated reaction products include from 2 to 10 (preferably 2 to 4) urethane and/or urea groups.
  • the aliphatic groups may be a simple alkane diol, such as 1,6-hexane diol, but it is preferred that the aliphatic groups be selected from polyether, polyester and polyether-ester groups.
  • Polyether groups are illustrated by tetramethylene glycol, polyester groups by the ester reaction product of two moles of ethylene glycol with one mole of adipic acid, and polyether-ester groups by the ester reaction product of two moles of diethylene glycol with one mole of adipic acid.
  • Appropriate diisocyanates may be aliphatic or aromatic, such as isophorone diisocyanate, 2,4-toluene diisocyanate and its isomers, and hexamethylene diisocyanate. Toluene diisocyanates are preferred, and this class of materials is well known in the art.
  • Diacrylate termination of the diisocyanates may be accomplished in various ways. Thus, one can form the higher molecular weight diisocyanates first, and then react with 2 molar proportions of hydroxy alkyl acrylate to thereby place one such unsaturated group on each available isocyanate group. These hydroxy alkyl acrylates may have from 2 to 6 carbon atoms in the alkyl group and are illustrated by hydroxy ethyl acrylate and by hydroxy propyl acrylate.
  • Urea groups may be incorporated into the polyurethane by reacting one mole of the previously described diisocyanates with one mole of hydroxy ethyl acrylate to provide an unsaturated urethane product containing a single unreacted isocyanate group. By then reacting two moles of this monoisocyanate with one mole of a diamine, such as butylene diamine, we obtain a polyurea polyurethane having two terminal acrylate groups.
  • Urea-containing diacrylates are further illustrated in U.S.-A-4,097,439.
  • the diglycidyl ethers of a bisphenol which are employed preferably have a 1,2-epoxy equivalency of about 2.0, but anything of at least 1.4 is useful herein. This merely means that the desired diglycidyl ethers are in admixture with monoglycidyl ethers which reduces the epoxy equivalency. These diglycidyl ethers, when of low molecular weight, can be used to form diacrylate (by adduction to form hydroxy acrylates). These, when used in combination with the diacrylate terminated polyurethanes, provide the moderate modulus coatings which have good hardness and toughness, as previously described.
  • bisphenol denotes a pair of phenolic groups linked together through an intervening divalent structure which is usually an alkylene group.
  • an intervening divalent structure which is usually an alkylene group.
  • acrylic unsaturation is best, but since the radiation character can vary, so can the specific character of the unsaturation.
  • Other useful ethylenic unsaturations are illustrated by methacrylic, itaconic, crotonic, allylic, and vinylic. These can be provided (using methacrylic unsaturation as illustrative) by reaction of isocyanate functionality with 2-hydroxyethyl methacrylate. Allylic unsaturation may be introduced using allyl alcohol in place of hydroxyethyl acrylate. Vinylic unsaturation may be introduced using hydroxy butyl vinyl ether in place of hydroxyethyl acrylate.
  • acrylate unsaturation has been referred to previously as illustrative and preferred.
  • Other radiation curable monoethylenically unsaturated groups may be used in its place in the manner illustrated for methacrylic unsaturation.
  • the radiation which effects cure will vary with the photoinitiator used. Even visible light may be employed using appropriate photoinitiators. These are illustrated by camphor quinone and coumarin which are used together with a tertiary amine, such as triethyl amine. Diphenylbenzoylphosphine oxide is useful in and near the ultraviolet range.
  • the coating composition preferably contains a photoinitiator which is usually a ketonic photoinitiator, such as about 3% of diethoxy acetophenone.
  • a photoinitiator which is usually a ketonic photoinitiator, such as about 3% of diethoxy acetophenone.
  • Other photoinitiators are also known, such as acetophenone, benzophenone, m-chloroacetophenone, propionphenone, thioxanthone, benzoin, benzil, anthraquinone, and the like.
  • the photoinitiators may be used singly or in mixtures and are present in amounts up to about 10% of the coating composition.
  • Various amines, such as diethyl amine may also be present, but are not needed herein.
  • the radiation-curable coatings which are provided in accordance with this invention may be used for adhesives or for the coating of flexible floor tiles, but are very unique when applied as topcoats for buffer-coated optical fibers, as previously explained. Regardless of the use of which the coating compositions of this invention are put, and regardless of the radiation energy used to cure the same, they possess the same combination of superior hardness and toughness which allows them to serve as topcoats on optical fibers.
  • the coatings of this invention when cured, possess a modulus which is generally in the range of 68950 to 137900N/cm 2 (100,000 to 200,000 psi) at room temperature. This is far too hard to serve as a coating which is directly in contact with the glass surface of the fibers.
  • the buffer coatings which are used have a modulus measured at room temperature which is less than about 10342 N/cm 2 (15000 psi).
  • the invention is illustrated by a series of coating compositions formulated by simple mixing of the components tabulated below.
  • the mixture is warmed to about 55°C. for 1 hour to dissolve all of the components.
  • component 1 is an adduct of two moles of 2-hydroxyethyl acrylate with one mole of a diisocyanate-terminated polyurethane made by adducting a mixture of toluene diisocyanates (80% 2,4-isomer and 20% 2,6-isomer) with a polytetramethylene glycol formed by polymerizing tetrahydrofuran to form a polyether diol having a molecular weight of 600-800.
  • the polyurethane formed by acrylating this diisocyanate has a molecular weight of about 1900 and includes an average of 5-6 urethane groups per molecular.
  • the du Pont product Adiprene L-200@ may be used.
  • auxiliary agents are useful in the above examples.
  • One function served by such agents is to provide surface lubricity, a nonessential function.
  • surface lubricity is enhanced using silicone oils in small amounts.
  • Examples 1 and 3 used 0.2% of Dow Corning fluid DC 57@ and 0.6% of Dow Corning fluid DC 190@. In examples 2 and 4, 0.07% of DC 57 was used with 0.13% of DC 190.
  • Example 4 also used 0.2% of N-beta-(N-vinylbenzylamino) ethyl-gamma- aminopropyl trimethoxy silane, monohydrogen chloride. None of these additions is regarded to be important.
  • the coating compositions in the Table 1 were used as a topcoat on buffer-coated glass fiber.
  • the optical glass fiber which was buffer coated had a diameter of about 125 flm and it was buffer-coated to a thickness of 125 pm using the low modulus buffer coating described in JA-A-22 36 38/83 referred to previously.
  • the buffer coating was made by reacting 4 moles of 4,4'-methylene bis(cyclohexyl isocyanate) with 2 moles of polyoxypropylene glycol of molecular weight 1000 and then reacting with 2 moles of 2-hydroxyethyl acrylate and then with one mole of polyoxypropylene diamine of molecular weight 230 in the presence of 3.4 moles of N-vinyl pyrrolidone and 917 moles of phenoxyethyl acrylate.
  • This mixture with 3% by weight of diethoxy acetophenone, is ultraviolet cured on freshly formed optical fiber.
  • Examples 3 and 4 are superior, and the result is surprising. This is because the viscosities in Examples 3 and 4 are lower than in Examples 1 and 2, respectively, and hence more favorable. At the same time, the cure is faster and the coefficient of thermal expansion below the glass transition temperature is lower, so less strain is placed on the glass fiber at low temperature.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Surface Treatment Of Glass Fibres Or Filaments (AREA)

Claims (12)

1. Durch Strahlung härtbare Überzugsmasse, die zum Aufbringen auf pufferbeschichtete optische Fasern geeignet ist, um einen haftenden Decküberzug mit größerer Zähigkeit und größerer Härte als die Pufferschicht aufzubringen, enthaltend: (1) 25 bis 70% (bezogen auf die Überzugsmasse) Polyurethan mit diethylenischen Endgruppen, das auch Harnstoffbindungen enthalten kann, wobei das Polyurethan auf einem Diisocyanat mit einem durchschnittlichen Molekulargewicht von 400 bis 5000 basiert; (2) 5 bis 40% (bezogen auf die Überzugsmasse) eines diethylenisch ungesättigten Esters eines Diglycidylethers eines Bisphenols, wobei der Ether eine 1,2-Epoxyäquivalenz von mindestens 1,4 und ein Molekulargewicht bis zu 1000 hat; und (3) 5 bis 30% (bezogen auf die Überzugsmasse) flüssiges, durch Strahlung härtbares, monoethylenisch ungesättigtes Monomer, wobei die Glasübergangstemperatur (Tg) des aus diesem Monomer hergestellten Homopolymers oberhalb 55°C liegt.
2. Überzugsmasse nach Anspruch 1, worin der Diglycidylether ein Diglycidylether von Bisphenol A ist und ein durchschnittliches Molekulargewicht von weniger als 400 hat.
3. Überzugsmasse nach Anspruch 1, worin das Polyurethan mit diethylenischen Endgruppen ein durchschnittliches Molekulargewicht im Bereich von 800 bis 2500 hat.
4. Überzugsmasse nach Anspruch 1, worin 5 bis 30% der Überzugsmasse aus einem flüssigen Monomer aus der Gruppe Dimethylacrylamid, N-Vinylpyrrolidon, Isobornylacrylat und Dicyclopentenylacrylat zusammengesetzt sind.
5. Überzugsmasse nach Anspruch 4, worin das flüssige Monomer, im wesentlichen aus N-Vinylpyrrolidon besteht.
6. Überzugsmasse nach Anspruch 1, worin die Polyurethane mit diethylenischen Endgruppen ein organisches Diisocyanat enthalten, welches das Reaktionsprodukt eines organischen Diisocyanats mit einem aliphatischen Molekül mit 2 mit Isocyanat reagierenden Wasserstoffatomen darstellt, wobei das Reaktionsprodukt 2 bis 10 Urethan- und/oder Harnstoffgruppen enthält.
7. Überzugsmasse nach Anspruch 6, worin die aliphatischen Gruppen aus Polyether-, Polyester- und Polyether-Ester-Gruppen ausgewählt sind.
8. Überzugsmasse nach Anspruch 7, worin das Polyurethan mit endständigen diethylenischen Gruppen aus einem Hydroxyalkylacrylat erhalten wurde, in welchem die Alkylgruppe 2 bis 6 Kohlenstoffatome enthält.
9. Überzugsmasse nach Anspruch 8, worin das Acrylat Hydroxyethylacrylat darstellt.
10. Überzugsmasse nach Anspruch 9, worin das Polyurethan Harnstoffgruppen enthält.
11. Überzugsmasse nach einem der Ansprüche 1 bis 10, wobei die Masse zusätzlich einen Photoinitiator enthält.
12. Optische Glasfaser, die mit einem Grundüberzug beschichtet ist, der einen Raumtemperatur-Modul bei 2,5% Dehnung von weniger als 10342 N/cm2 (15000 psi) hat, und die weiterhin als Deckschicht einen durch Strahlung ausgehärteten Überzug der Überzugsmasse nach einem der Ansprüche 1 bis 11 trägt.
EP83112164A 1982-12-28 1983-12-03 Äussere Anstrichmittel für optische Fasern mit einer Pufferschicht Expired EP0114982B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US453972 1982-12-28
US06/453,972 US4472019A (en) 1982-12-28 1982-12-28 Topcoats for buffer-coated optical fiber using urethane acrylate and epoxy acrylate and vinyl monomer

Publications (3)

Publication Number Publication Date
EP0114982A2 EP0114982A2 (de) 1984-08-08
EP0114982A3 EP0114982A3 (en) 1984-08-29
EP0114982B1 true EP0114982B1 (de) 1987-06-10

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EP83112164A Expired EP0114982B1 (de) 1982-12-28 1983-12-03 Äussere Anstrichmittel für optische Fasern mit einer Pufferschicht

Country Status (4)

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US (1) US4472019A (de)
EP (1) EP0114982B1 (de)
CA (1) CA1201840A (de)
DE (1) DE3371985D1 (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
LT3310B (en) 1988-12-02 1995-06-26 Basf Lacke & Farben Liquid, radiation-cured coating composition for glass surfaces, process for coating, optical glass fibre
LT3330B (en) 1989-04-29 1995-07-25 Basf Lacke & Farben Liquid, radiation-cured coating composition for glass surfaces
US6187835B1 (en) * 1997-06-18 2001-02-13 Dsm N.V. Radiation-curable optical fiber coatings having reduced yellowing and fast cure speed

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US4691989A (en) * 1983-09-01 1987-09-08 American Telephone And Telegraph Company, At&T Bell Laboratories Optical fiber cable
JPS6083907A (ja) * 1983-10-14 1985-05-13 Nitto Electric Ind Co Ltd 光学ガラスフアイバ用被覆材料
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US4849462A (en) * 1983-11-10 1989-07-18 Desoto, Inc. Ultraviolet-curable coatings for optical glass fibers having improved adhesion
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US4572610A (en) * 1984-05-21 1986-02-25 Desoto, Inc. Optical fiber buffer coated with halogenated dihydroxy-terminated polybutadienes
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DE3371985D1 (en) 1987-07-16
EP0114982A2 (de) 1984-08-08
EP0114982A3 (en) 1984-08-29
US4472019A (en) 1984-09-18
CA1201840A (en) 1986-03-11

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